Synthetic resinous compositions



Patented Apr. 10, 1945 SYNTHETIC RESINOUS COMPOSITIONS Maynard C. Agens, Schenectady, N. Y., asslgnor to General Electric Com New York No Drawing.

This invention relates to synthetic resinous or resin-forming compositions derived from partial esters of alpha-unsaturated polycarboxylic acids and to a process of preparing them. It is concerned particularly with the preparation of resinous reaction products of the above type capable of polymerizing to an insoluble, infusible state.

An object of thepresent invention is to produce novel resinous materials which can be used in the preparation of coating, impregnating, and molding compositions and. which comprise alcoholpolybasic acid esterification products capable of being more readily hardened by' oxidation or polymerization due to the presence of terminal double bonded groups in the esterified product.

Other objects of my invention will become apparent from the following description of my invention.

The present invention is based on'my discovery that when certain alpha-unsaturated acids such as maleic acid, or the mono-esterification reaction products of alcohols and these alphaunsaturated polybasic acids are treated with cyclic amines'selected from the group consisting of pyridine and its homologues and hydrocarbon derivatives, i. e., quinoline, nicotine, piperidine, etc., large quantities of carbon dioxide are given off with the resultant formation of decarboxylated resinous masses which are much more readily hardened by polymerization or oxidation and hence are faster air-drying than are the ordinary alpha-unsaturated polybasic acid esteriflcation products.

Any of the monoor poly-hydric alcohols used in resin manufacture may be employed in the practice of my invention including the saturated monohydric alcohols such as methyl, ethyl, propyl,

butyl, etc., alcohols, the dihydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, etc., the trihydric alcohols such as glycerine, etc., or mixtures of two or more of these alcohols.

I prefer to use the monoor di-hydric alcohols or alcoholic mixtures comprising major proportions of these alcohols, as the resin-forming reactions involving such alcohols are more easily controlled. However, provided adequate precautions are taken to control the rate 01' reaction pany, a corporation of Application December 13'. 1941, Serial No. 422.905

15 Claims. (01.260-) and to carry the initial mono-esterlflcation reaction to substantial completion before the introduction oi the decarboxylating agent, the higher polyhydric alcohols such as glycerine, pentaerythritol and the like may be used alone.

As the polybasic acid reactant I prefer maleic or tumaric acids since the free carboxyl groups in the mono-esters of both of these acids are readily decarboxylated to form terminal groups. Other alpha-unsaturated acids which may be used and which are decarboxylated when treated with the above amines are itaconic acid and aconitic acid. However, the number of'terminal CHFlgroups obtained by the decarboxylation of these I latter acids is correspondingly smaller and is dependent upon the extent to which the carboxyl groups have entered into the esterification reaction.

The following examples will serve to illustrate in greater detail typical resinous ,compositlons falling within the scope of my invention.

EXAMPLE 1 To compare the products obtained by reacting glycol with maleic anhydride with and without the addition of pyridine, the following resins were prepared. v

(A) Straight diethylene glycol-maleate resins.

(B) Pyridine-modified diethylene glycol-maleate resins.

. boxylation must necesseri droxyl groups, I D lt Resin lilo. 3

7 Ba nf Composition, Cooklngsehedule g: $33 Colcrvalue 294g.maleic anhydridc.. J 04 hr. 120-130 o. m 318g. disthylena' hn.,140150 (5., a 457 22.2 Rcd. ycol. waldo-200C.) I v c.c.pyrid ins v i Resin No'. 4'

H: I 881M311.- ,1 Cooking schedule $3: $33 Color hydrid wa 105* or 1 hr. 10003-1118 lane lo-.100" 6., and" -1 500 25.8 glycol. 2059. lbs-mp I,

In and i -the pi -asst added to a mixture' otf the remaining'"ingredients at the beinning ofi the' reaction.- The cooking schedules for the pyridinermodified resins were necessarily shorterzan'd atlower temperatures because oi the faster rate oi'reactionj'of 1358 modified resins.

'. It canbes'een from. the"above that thesaponiflcatiori-valu'e of thegstraightj diethylene glycol male'ate resin does-not change with the change in size oi the batch-nor the heating schedule. However, when a decarboxylating' agent such as pyridine is" used there is a"c o'nsiderable change in saponification value, depending upon the ratio of pyridine to size of batch. and upon the heating schedule which controls the rate of loss of COzas well as the -lcss of water;

Tests conducted to determine the air-drying and baking characteristics oi! these. two types of resins indicated that theintrodu'ction oi the more reactive terminal double bonds by use oi! a decarboxylating agent makes the resin much more reactive with oxygen; Although the introduction of the CH:=CH-, groups does not change the total unsaturation oithe resin, it does change the type oil. .unsaturation' in that these double bonds areterminal and hence more reactive. Solutions oi the diethylene glycol maleate resins made with and without pyridine were prepared and to each was added 4 per cent by weight of a metallic 'drier, specifically cobalt acid maleate. based on the 'wfeight of the resin. In four hours a film-Of the resin made with pyridine had dried when no'jperoxide was uaddedj the resin made without the use of pyridine seemed to bake faster at 100 C. This observation can be explained by the fact that a balanced jiormula was used in the preparationbt these resins and hence decar- 1yv }l ""unreacted hytionable, he retried clv Preferably, as is'shown pics, the decarboxylating agent is added to the alcohol-polybasic acid reaction mass aiter the esterification reaction has proceeded to a point where the mass has an acid value 01' about onedride and 1060 parts by weight of diethylene glycol was introduced into a closed reaction vessel bon dioxide. Thealcohol acid mixture was heat V In any of the. above formulations, all or part. of maleic anhydride may beireplaced |by ma.lelc v round objec- 7 provided with an inlet ior. introducing an inert gaseous atmosphere such. 'as nitrogen into the vessel and aside arm 'condenser ior condensing any water given 08 during the reaction. The condenser was in turn connected to a water trap for collecting the condensate, a jdrier' jior removing the. last traces of water vapor from the .eiiluent gas, and a soda lime tube'ior absorbing car-'- reacted in the inert atmosphere to'an acid value oi 233. Ten parts pyridine were then added to this esterified' product. The reaction was continned in an inert atmosphere for 20 minutes up to a temperature of C., 5 hours at 150-160? C. and 1% hours at 180-196C. to produce a reddish, viscous resin' syrup having an acid value 01' 30. A largeamount voi carbon dioxide was given off during thereaction, as was evidenced by an increase of 120 gms. inthe weight of the soda lime tube.

Extinct: 3.

A mixture of 294 parts maleic-anhydride and 318 parts diethylene "glycol was heated i'orabout 20 minutes at C. in an apparatus such as that used in Example 2. The 20 minute reaction period was suiiicient to carry the initial esterification or anhydride reaction substantially to com' pletion with the iormation 'ot a mixture containing a. large proportion oi the monoglycol ester of maleic acid. One part pyridine was added and the reaction continued for hour at 200 C. and 1% hours at200-210" C. The product was a "reddish, resinous syrup with an acid value of 34.3. The increase in weight of the soda lime tube indicated that 27 gms. CO: were given off during the reaction.

As each of theabove formulations call for a balance, at the beginning of the reaction, of

hydroxyl and carboxyl groups, the final decarboxylated product must' contain an excessof hydroxyl groups. To avoidthis result, the resins may be prepared using an excess 01 ,carbo-xyl groups, 1. e., polycarboxylic acid, as is shown in the following example. i

A mixture 01294 partsmaleic anhydride and 265 parts diethylene glycolwere reacted together under the conditions set torth in Example 2 to an acid value 01312. Five-parts pyridine were added and the reaction continued for one .hour at 190-197? C; The syrupy-product had an acid value of 57.2. A bout o grams acids however are "not 'decarboxylated when.

of CO: were given heated with pyridine or the other decarboxylated agents used in the practice of my invention and therefore impart to the final resinous products those characteristics possesed by ordinary alkyd resins prepared from these acids.

In the above examples, the decarboxylating agent, specifically pyridine, was used in'amounts ranging from 0.3- per cent by weight based on the weight of the alpha-unsaturated acid, specifically maleic anhydride; that is, from 0.004 to 0.08 mol pyridine per mol of maleic anhydride. The rate of decarboxylation will depend on the concentration of the decarboxylating agent in the reaction mixture. Preferably from 0.01 to 0.1 mol of the decarboxylating agent per mol of acid is used. The decaitboxylating agent apparently removes only one of the carboxyl groups in the polybasic acid even 'thoughfneither has undergone esterification with the alcohol. This is indicated by the fact that when equimolecular proportions of maleic acid and pyridine are heated together about 1 mol of CO: is given off and the residue left in the reaction vessel consists of a thick resinous mass of polymerized pyridine acrylate and a heavy liquid layer oi monomeric pyridine acrylate.

Exsurts 5 An identification of the intermediate and final esters and some free acid were also present. The

cloudy liquid which remained after the separa- I tion of the crystalline maleic acid and which contained the monoand di-esters and had an acid value of 300 was heated with a decarboxylating agent, specifically pyridine. About 15 parts by weight of CO: were liberated from each 100 parts of the ester mixture during the heating step. The distillate collected from the reaction was washed with dilute hydrochloric acid and water to remove the pyridine and then taken up in either. After evaporation of the ether, a light yellow liquid remained. This liquid was found to contain a large proportion of butyl acrylate.

It is tobe understood that the free acids need not be separated from the ester mixtures before in the soluble, fusible form, may be employed as such or in solution in the preparation of paints, lacquers, baking enamels, impregnating compositions, insulating compositions, laminated products, etc. suitablesolvents for the resins include acetone, diacetone, chlorinated benzene,

ethyl acetate, benzeneor toluene-alcohol mixtures, etc. In any of these applications the resins may be modified by the addition 01' other materials including other resins, e. g., alkyd resins, aminoplast resins, vinyl or acrylic resins, polyvinyl acetals, or the like; cellulose derivatives, e. g., cellulose esters and ethers; plasticizers, e. g., triphenyl phosphate, tricresyl phosphate, castor oil, glycerine, and the like; orwith fillers, e, g., wood flour, paper, glass fiber, sand, asbestos, and the like. The decarboxylated esters may be coor inter-polymerized with other polymerizable substances such as the vinyl com-, pounds, 1. e., vinyl chloride, vinylacetate, etc., the acrylic and methacrylic acid esters, or the diallyl esters of phthalic acid or succinic acid and the like.

When the resins, are used in compositions intended for air-drying applications, suitable metallic driers such as are used in air-drying varnishes may be incorporated into the compositions to accelerate hardening thereof. Likewise polymerization catalysts may be used to acceler- -ate the conversion of these resins into the insoluble, iniusible form. Benzoyl peroxide, hy-

peroxide, lauroyl peroxide, lauryl peroxide, stearyl peroxide, peroxides of tetrahydro-furane, ascarido], and calcium peroxide are examples of catalysts of this type.

What I claim as new and desire to secure b Letters Patent of the United States is:

1. A resinous composition comprising a polymerlzable, decarboxylated, partially esterifled alpha-unsaturated polycarboxylie acid obtained by heat-reacting an alpha-unsaturated polycarboxylic acid with an alcohol in the presence of from about 0.004 to 0.1 mol, per mol of alpha-unsaturated polycarboxylic acid, of a cyclic amine capable of dccarboxylating partial esters of said alpha-unsaturated acid, the said cyclic amine being selected from the group consisting of pyridine, quinoline, nicotine, and piperidine and their homologues.

2. A resinous composition comprising the insoluble, polymerized product of claim 1.

3. A resinous composition comprising a decarboxylated esteriiication product obtained by heating an ester of an alcohol and an alpha-unsaturated polycarboxylic acid in which about onehalf of the carboxyl groups of the unsaturated acid are esteriiled with the alcohol with a cyclic amine selected from the group consisting of pyridine, quinoline, nicotine, and piperidine and their homologues to eflect decarboxylation of the meaterifled carboxyl groups of said ester, the said amine being present in the mol ratio of from 0.004 to 0.1 mol per amineper molof alphaunsaturated polycarboxylic acid.

4. The insoluble, iniusible, oxygen-converted product of claim 3. p

5. A resinous composition comprising the product of decarboxylatingan esteriflcation product of approximately equimolecular proportions of an alcohol and an alpha-unsaturated polycarboxylic acid containing about one free carboxyl group per molecule of polycarboxylic acid by heating said esteriilcation product with a cyclic amine selected from the group consisting of pyridine, quinoline, nicotine, and piperidine and their homologues in the mol ratio of from 0.004

to 0.1 mol cyclic amine per mol of alpha-unsaturated acid. 1

6. A resinous composition comprising a decarboxylated glycol mono-ester of an alpha-ununlisted polyearboxyiie acid obtained by de'-,

carboxyiatins a glycol mono-ester of an alphaunsaturated poiycarboxylic acid by heating said ester-in the presence or from 0.01% 0.1 mol of a decarboxylating agent selected from the group consisting of pyridine, quinoiine, nicotine, and piperidine and. their homologues per mol alphaunsaturated polycarboxylic acid. 7. A resinous composition'comprising a decarboxyiated glycol mono-maieate obtained by decarboxyiating glycol mono-maleate .by heating said mono-maleate in the presence at from 0.01

to 0.1 mol oi! a cyclic amine selected from the group consisting of pyridine, quinoline, nicotine,

and piperidine and their'homoiogues per mol oioi the carboxyl groups have been esteriiied to cause decarboxyiation oi the unesterifled carboxyl groups of said alpha-unsaturated polycarboxyllc acid','the said decarboxylating agent being present in that amount corresponding to from 0.01 to 0.1 moi per moi of alpha-unsaturated polycarboxylic acid. I

9. A polymerizable resinous composition comprising the reaction product obtained by heating irom about 0.01 to 0.1 mol of an amine selected from the group consisting of pyridine, quinoline, nicotine, and .piperidine and their homologues with one mol o i"a gly'coi mono-ester an aipha-imsaturated polycarboxylic acid to e1- iect a decarboxyiatio'n of unesterified carboxyl groups in saidmono-ester.

' mol per moi poiycarboxylic acid of an amine sci 10. A pclymerizable resinous composition comprising the productot heat reaction of from bout 0.01 to 0.1 molot'a cyclic amine selected from the group ct -pyridine, quinoline, nicotine,

7 CERTIFICATE OF conmzcrrofi.

human 0. seats and piperidine andthcir hcmologues with one moi of a, mono-ester oi glycol and maleic acid to effect a decarboxylation of unesteriiled carboxyi groups in said mono-ester.

11. The method which comprises heat-reacting an alcohol with an-alpha-unsaturated polycarboxylic acid until the initial mono-esteriiication reaction has taken place and decarboxylating the esteriiied product by heating said esteriiication product with from 0.01 to 0.1 moi, per moi 01' polycarboxylic acid, of a cyclic amine selected i'rom the group consisting of pyridine, quinoiine, nicotine, and piperidine and their homologues.

12. The method which comprises heat-reacting glycol with maleic anhydride in an inert atmosphere until the acid value of the condensation product is about-one-half that calculated for the original unreacted mixture, adding from 0.004 to 0.06 mol pyridine per mol maleic anhydride to said condensation product and heating the resultant mixture to cfl'ect a decarboxylation. oi! unesteriiied carboxyl groups present in said conden sation product with the resultant formation of a soluble, fusible, polymerizabie resin.

13. A poiymerizable resinous product obtained heating a mixture of ingredients comprising a mono-ester of an alcohol and an alpha-unsaturated polycarboxylic acid and from 0.004 to 0.08

iected from the group consisting of pyridine, quinoline, nicotine, piperidine, and their homologues to effect decarboxylation of the tree carbonyl groups oi said mono-ester.

14. A resinous product obtained by decal-boxylating free carboxyl groups in a mono-ester oi diethyiene glycol and an alpha-unsaturated polycarboxyiic acid by heating said mono-ester with from 0.3 to 5 per cent by weight of pyridine based v on theweight of the poiycarboxylic acid.-

15. A resinous product obtained by decarboirylating tree carbonl groups in a, di-ethylene glycol mono-ester of maieic acid by heating saidmonoester with from 0.004 to 0.06 mol pyridine per mol maieic acid.

.iipri l 10,150

it islhereib ylcertified that error appears inthe printed specification I 'o f the-above numberedfpatent requiring correction as followssi age 2, sec- "0nd: column, slinefli iixample li, after -"'benzo1c"*-1nsert :-'-aci.ds -;fpage f1net 'coiiairl n; lineij j, Example 5,'for "either" need and second Q column, line" 58', claim-5, strike "per" first oeourrence g. g ge-l ea ond column, us 2', 1a1mi1 after Perfect" insert-"4%;-

ni e said Letters" Patentfsh'ould be read with this correctionlthereinjhatthe Q (seal):-

"semen 1w contemtothe record of the we in thef'rateneforri e.

"signe -a ds aledjuiis'19th day or .June', 11.1). 111905 I K Braz er unlisted polyearboxyiie acid obtained by de'-,

carboxyiatins a glycol mono-ester of an alphaunsaturated poiycarboxylic acid by heating said ester-in the presence or from 0.01% 0.1 mol of a decarboxylating agent selected from the group consisting of pyridine, quinoiine, nicotine, and piperidine and. their homologues per mol alphaunsaturated polycarboxylic acid. 7. A resinous composition'comprising a decarboxyiated glycol mono-maieate obtained by decarboxyiating glycol mono-maleate .by heating said mono-maleate in the presence at from 0.01

to 0.1 mol oi! a cyclic amine selected from the group consisting of pyridine, quinoline, nicotine,

and piperidine and their'homoiogues per mol oioi the carboxyl groups have been esteriiied to cause decarboxyiation oi the unesterifled carboxyl groups of said alpha-unsaturated polycarboxyllc acid','the said decarboxylating agent being present in that amount corresponding to from 0.01 to 0.1 moi per moi of alpha-unsaturated polycarboxylic acid. I

9. A polymerizable resinous composition comprising the reaction product obtained by heating irom about 0.01 to 0.1 mol of an amine selected from the group consisting of pyridine, quinoline, nicotine, and .piperidine and their homologues with one mol o i"a gly'coi mono-ester an aipha-imsaturated polycarboxylic acid to e1- iect a decarboxyiatio'n of unesterified carboxyl groups in saidmono-ester.

' mol per moi poiycarboxylic acid of an amine sci 10. A pclymerizable resinous composition comprising the productot heat reaction of from bout 0.01 to 0.1 molot'a cyclic amine selected from the group ct -pyridine, quinoline, nicotine,

7 CERTIFICATE OF conmzcrrofi.

human 0. seats and piperidine andthcir hcmologues with one moi of a, mono-ester oi glycol and maleic acid to effect a decarboxylation of unesteriiled carboxyi groups in said mono-ester.

11. The method which comprises heat-reacting an alcohol with an-alpha-unsaturated polycarboxylic acid until the initial mono-esteriiication reaction has taken place and decarboxylating the esteriiied product by heating said esteriiication product with from 0.01 to 0.1 moi, per moi 01' polycarboxylic acid, of a cyclic amine selected i'rom the group consisting of pyridine, quinoiine, nicotine, and piperidine and their homologues.

12. The method which comprises heat-reacting glycol with maleic anhydride in an inert atmosphere until the acid value of the condensation product is about-one-half that calculated for the original unreacted mixture, adding from 0.004 to 0.06 mol pyridine per mol maleic anhydride to said condensation product and heating the resultant mixture to cfl'ect a decarboxylation. oi! unesteriiied carboxyl groups present in said conden sation product with the resultant formation of a soluble, fusible, polymerizabie resin.

13. A poiymerizable resinous product obtained heating a mixture of ingredients comprising a mono-ester of an alcohol and an alpha-unsaturated polycarboxylic acid and from 0.004 to 0.08

iected from the group consisting of pyridine, quinoline, nicotine, piperidine, and their homologues to effect decarboxylation of the tree carbonyl groups oi said mono-ester.

14. A resinous product obtained by decal-boxylating free carboxyl groups in a mono-ester oi diethyiene glycol and an alpha-unsaturated polycarboxyiic acid by heating said mono-ester with from 0.3 to 5 per cent by weight of pyridine based v on theweight of the poiycarboxylic acid.-

15. A resinous product obtained by decarboirylating tree carbonl groups in a, di-ethylene glycol mono-ester of maieic acid by heating saidmonoester with from 0.004 to 0.06 mol pyridine per mol maieic acid.

.iipri l 10,150

it islhereib ylcertified that error appears inthe printed specification I 'o f the-above numberedfpatent requiring correction as followssi age 2, sec- "0nd: column, slinefli iixample li, after -"'benzo1c"*-1nsert :-'-aci.ds -;fpage f1net 'coiiairl n; lineij j, Example 5,'for "either" need and second Q column, line" 58', claim-5, strike "per" first oeourrence g. g ge-l ea ond column, us 2', 1a1mi1 after Perfect" insert-"4%;-

ni e said Letters" Patentfsh'ould be read with this correctionlthereinjhatthe Q (seal):-

"semen 1w contemtothe record of the we in thef'rateneforri e.

"signe -a ds aledjuiis'19th day or .June', 11.1). 111905 I K Braz er 

